US2676166A - Polymeric quaternary ammonium compounds - Google Patents

Polymeric quaternary ammonium compounds Download PDF

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US2676166A
US2676166A US279937A US27993752A US2676166A US 2676166 A US2676166 A US 2676166A US 279937 A US279937 A US 279937A US 27993752 A US27993752 A US 27993752A US 2676166 A US2676166 A US 2676166A
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quaternary ammonium
copolymer
oxirane
water
acid
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Webers Vincent Joseph
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3209—Epoxy compounds containing three or more epoxy groups obtained by polymerisation of unsaturated mono-epoxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/06—Protein or carboxylic compound containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/07—Organic amine, amide, or n-base containing

Definitions

  • This invention relates to polymeric quaternary ammonium compounds and to a process of preparing same and, more particularly, to new poly meric quaternary ammonium compounds.
  • Polymeric compounds containing quaternary ammonium hydroxide or salt groups are b'ecom-" ing of increasing technical interest in various applications such as, for example,acid -dyeable adjuvants to fiber-forming polymeric materials.
  • An object of the present invention is to pro vide an economic processoi preparing polymeric quaternary ammonium 'comp'ounds'from readily available polymers in one operation.
  • a further object is to provide new polymeric quaternary ammonium compounds.
  • the above objects are accomplished according to the present invention by reacting a copolymer of a vinylidene monomer free from epoxy groups and an ethylenically unsaturated epoxy -gro'up containing monomer, with a tertiary monoamine and either water or an acid or a combination of both.
  • the resulting product is a copolymer con.- taining polymerized units of a vinylidene monomer free of epoxy groups and polymerized units of an ethylenically unsaturated epoxy monomer in which latter units the oxirane ring has opened to alpha-hydroxy-beta-quatemary ammonium groups.
  • the resulting compound can also contain unreacted epoxy groups.
  • polymeric quaternary ammonium compounds are characterized by having at least 0.3% nitrogen, by weight, and a molecular weight of at least 500.
  • the copolymer should have .a molecular weight above about 500 and contain from about 0.3% to about 8%, by weight, of oxirane oxygen and it should be reacted with a tertiary amine and with a compound HX in which X is hydroxyl or an anion, the tertiary amine and HK compound each being used in amounts of at least 0.25 equivalent per oxirane oxygen atom in the epoxy-containing copolymer.
  • an epoxygroup also called oxirane group
  • oxirane group is the group 7
  • the oxygen atom which is part of the oxirane group is re to, Q iIane o yg n. 4
  • RcN is a tertiary monoamine
  • ED! is a compound wherein X is hydroxyl or an anion, i. e., HX is water or an inorganic or organic acid.
  • the polymeric compounds of this invention are quaternary ammonium hydroxides or salts, depending on whether the reactant I-lX is water or an'facid. They are resinous materials of viscous to semi-solid consistency and of indefinite melting point. Most of these compounds are soluble in dilute aqueous acids, e. g., aqueous acetic acid, and many of them are soluble in'water; In some instances, however, particularly when the starting copolymer has a low oxirane oxygen content, i. e., a low proportion of polymerized epoxy monomer, and/or when the degree'of substitution by the tertiary amine is low, the polymer is insoluble or only slightly soluble in dilute acids. In all cases, nevertheless, the polymers contain at least 0.3%, by weight, of nitrogen and this minimum proportion is necessary for significant modification of the starting copolymer. Preferably, the polymers contain between 0.5% and 5% of nitrogen.
  • the polymeric quaternary ammonium compounds of this invention have a. plurality of pairs of adjacent extralinear carbon atoms, one carbon atom of a pair carrying a quaternary ammonium radical and the other a hydroxyl group. Otherwise expressed, these compounds have a plurality of extralinear units containing the wherein Q is a quaternary ammonium radical. As previously stated, these compounds are further characterized by containing at least 0.3% nitrogen, by weight, and having a molecular weight of at least 500.
  • Preparation of these polymeric quaternary ammonium compounds can be conveniently carried out as follows: A solution, preferably at 25-75% m m tlQP: 9: 2 p q P9 Y in an organic solvent which is substantialy inert to the reactants used under the operating conditions, is treated with the tertiary amine, the amount of the latter being at least 0.25 equivalent, and preferably between 0.5 and 5 equivalents, per epoxy group. If desired, the amine is dissolved, preferably at -50% concentration, in an inert organic. solvent.
  • reaction mixture water or an organic or inorganic acid in; amounts of at least 0.25 equivalent, and preferably between 0.25 and 5 equivalents, per epoxy group. If--desired, both water and an acid can be used simultaneously.
  • the reaction mixture is usually, but. not necessarily, diluted to about solids by addition of an inert organic solvent, preferably one that is partly or completely miscible with water, such as methyl ethyl ketone or dioxane.
  • an inert organic solvent preferably one that is partly or completely miscible with water, such as methyl ethyl ketone or dioxane.
  • the re- 4 g. of methyl ethyl ketone was mixed with 2.36 g. of trimethylamine in 12.2 g.
  • AGE/VAc allyl glycldyl ether/vinyl acetate action mixture is thenheld .at a suitable tem- 2o reaction product in dilute aqueous acid, e. g., 10%
  • reaction product can .be. tested qualitatively orlquantitatively for the presence. of nitrogen.
  • reaction product shouldcontainatleast 0.3% nitrogen.
  • reaction product is convenientlyisolated by either of two general procedures: (a) All solvents and volatile amine are removed by vacu-. umdistillation at low or. moderate temperature, eg.,v C. When the residuebecomes quite. viscous, some water may be added to thin it. out. and the distillation is .continueduntilthe residue reaches or' approaches the theoretical dry weight.
  • the polymeric quaternary ammonium .baseor salt. is preferably stored as a 20-40% solution in water or diluteacetic ,acid, or as an organic solvent solution.
  • (b) The reactionmixture is poured in':.' to a poor solventfor the quaternary ammonium" polymer, such as. ether, and theprecipitated nitrogen-containing polymer is stirred with ad ditional ether. The process may be repeated by redissolving the polymer inan appropriate sol vent andreprecipitating it with ether. The so].-
  • the starting material was an allyl glycidyl ether/vinyl acetate copolymer 'havinga mo'lecurlar weight of 3500 and containing 9.3%- ofpoly ind-9 g. methyl ethyl hetone, m-ixed with 35.4 ,g. trimethylamine (eq.;ratio 1.111) in 180 g. isopropylacloholand 32.2.;g.;-acetic acid (eq. ratio 1.11). .Reacted. A days, room temperature. Theproduct. -was: wateresoluble and neutral.
  • oxirane oxygen 192g. v(0.206 .oxirane eq.) in 108 g. dioxane, mixed with 8.74 'g. trimethylamine merized allyl glycidyl ether (118% oxyj gen).
  • Example VI AGE Wm (M'; w: about 1000, 913% AGE, 1.3% Y oxirane ox eer-gmr-wg.---(*0.'0111 oxirane eq.)
  • Ezcample XXV i-vinylcyclohexene monoepoxide/vinyl acetate copolymer (M. W. 2200, 9.3% d-vinylcyclohexene monoepoxide, 1.2% oxirane oxygen), 10.0 g. (0.0075 oxirane eq.) in 10.0 g. methyl ethyl ketone, mixed with 0.89 g. trimethylamine (eq. ratio 2:1) in 4.6 g. isopropyl alcohol and 1.2 g. acetic acid (eq. ratio 2.66:1). Added 20.7 g. dioxane and reacted 4 hours at 80-85 C. The product was almost completely soluble in water and dilute acetic acid.
  • Example XXVI Glycidyl methacrylate/butyl methacrylate copolymer (M. W. 3500, 30% glycidyl methacrylate, 3.38% oxirane oxygen), 10.0 g. (0.0211 oxirane eq.) in 10.0 g. methyl isobutyl ketone, mixed with 2.95 g. trimethylamine (eq. ratio 2.13:1) in 15.25 g. isopropyl alcohol and 0.65 g. water (eq. ratio 1.7:1). Reacted 2 hours, room temperature. Product was water-soluble.
  • the present invention broadly comprises reacting a copolymer of a vinylidene monomer free from epoxy groups and an ethylenically unsaturated epoxy-group containing monomer, with a tertiary monoamine and water or an acid, to form a polymeric quaternary ammonium compound containing at least 0.3% nitrogen and having a molecular weight of at least 500.
  • Such copolymers offer a number of important technical advantages in the preparation of polymeric quaternary ammonium compounds.
  • polymers of the type defined above can be obtained which combine high molecular weight with high oxirane oxygen content, a combination which is not possible when using epoxy polymers such as, for example, those prepared by condensing dihydric phenols and epichlorohydrin in alkaline solution.
  • epoxy polymers such as, for example, those prepared by condensing dihydric phenols and epichlorohydrin in alkaline solution.
  • the starting copolymers are in general easy to prepare by wellknown methods and, in many cases, they ofi'er substantial economic advantages since the bulk of the weight can be derived from a cheap, readily available vinylidene monomer.
  • the epoxy copolymer should contain at least about 0.3% of oxirane oxygen since, if the oxirane oxygen content is appreciably below that value, there will not be enough epoxy groups present to react effectively with the tertiary amine.
  • the polymerizable epoxy compound is present in the polymerization mixture in proportions such that the resulting copolymer has appreciably more than 8% of oxirane oxygen, then the polymerization becomes diflicult to carry out and control as, in.
  • the starting copolymer contains between 0.6% and 7% of oxirane oxygen. copolymers within the desired range of oxirane.
  • oxygen content are generally obtained when the weight ratio of polymerized epoxy compound to polymerized oxirane-free unsaturate is within the range of 3:97 to 60:40.
  • the molecular weight of the copolymer is de sirably above 500 in order that the final products have the desired polymeric properties. As a consequence, the molecular weight of the final products will be at least 500. Preferably, the molecular weight of the copolymer is in the range of from about 1000 to about 10,000.
  • the preferred copolymers have at least two epoxy groups per molecule.
  • the epoxide copolymers are prepared by free radical-initiated polymerization according to known methods and with known free radicalproducing initiators. to avoid conditions which would tend to open or otherwise destroy the epoxy groups, such as the presence of strong acids.
  • the monomers are in general used in relative amounts within the range of 5 to 75 parts of oxirane-con taining unsaturate for to 25 parts of oxiranefree unsaturate.
  • Two or more comonomers of each type can be used provided the above ratios are observed.
  • these copolymers are made from monomers having only one ethylenic, carbon to carbon double bond, to
  • copolymers should obviously be prepared from monomers free from groups containing active hydrogen capable of reacting with an epoxide group.
  • the preferred starting materials because they give the most generally useful polymeric quaternary ammonium compounds, are the copolymers of allyl glycidyl ether with polymerizable vinylidene compounds, i. e., compounds having a terminal methylene group attached through a double bond-to the adjacent carbon atom.
  • These preferred materials include the copolymers of allyl glycidyl ether with the vinyl halides, e. g.,
  • vinyl chloride vinyl fluoride
  • vinyl esters of monocarboxylic acids e. g., vinyl acetate, vinyl 1 methacrylamide
  • Any tertiary monoamine may be used to prepare the polymeric quaternary ammonium compounds, although it is preferred to use an amine of relatively low molecular weight, e. g., one containing a total of between 3 and 24 carbon atoms.
  • the preferred amines are those in which the radicals attached to the amino nitrogen each contain from 1 to 6 carbon atoms, inclusive. Still more preferred are the ethylenically saturated amines containing only carbon and hydrogen in addition to the amino nitrogen.
  • Suitable amines in addition to those shown in the examples, include tri-n-propylamine, tri-n-octylamine, N,N-
  • the tertiary amine should preferably have a 'basicity equivalent to an ionization constant of at least 1 10.
  • weak bases it is advantageous to use an acid rather than water as the third reactant, in order to increase the reaction rate and bring the reaction time down to a convenient value, and to avoid degradation of the polymer which might be caused by prolonged heating.
  • the amine should be used in amount of at least 0.25 equivalent per oxirane oxygen atom in the epoxide-containing copolymer. Preferably, it is used in amounts between 0.5 and 5.0 equivalents per epoxy group. More can be used, if desired, but this is uneconomical and unnecessary.
  • the third reactant is water or an acid, leading to a polymeric quaternary ammonium hydroxide or salt.
  • Any inorganic or organic acid can be used, including for example, hydrochloric, phosphoric, sulfuric, acetic, propionic, benzoic, and lactic acids. It is advantageous to use a cheap and common acid.
  • the acid is a monobasic acid having a dissociation constant of at least 1X10- An amine carbonate can sometimes be used advantageously.
  • Water and an acid can be used simultaneously. The water and/or the acid should be used in amounts of at least 0.25 equivalent per epoxy group, and preferably between 0.5 and 3 equivalents.
  • the acid in amounts between 0.5 and 1.5 equivalents per equivalent of amine, since a large excess of acid relative to the amine might cause excessive opening of the epoxy groups in the polymer. Water can be used in large excess relative to the amine, although there is usually no advantage in doing so.
  • the third reactant i.e., water or acid
  • the third reactant i.e., water or acid
  • the process is carried out conveniently by bringing the three reactants in contact and allowing the reaction to proceed, preferably at a temperature in the range of 0 C. to 150 C., and still more preferably in the range of 15 C. to 100 C.
  • the reaction time depends on the temperature to a considerable extent.
  • the reaction rate when weakly basic amines are used is accelerated by using an acid as the third reactant; rather than water.
  • the progress of the reaction can be droxide or salt group.
  • the starting material is a copolymer containing as 10 followed by testing the solubility of the product in dilute acid or water.
  • the product, after removal of the unchanged amine can be tested qualitatively or quantitatively for the presence of nitrogen.
  • the final product should contain at least 0.3% of nitrogen.
  • the products of this invention are polymers having a plurality of pairs of adjacent extralinear carbon atoms, one carbon atom of a pair carrying quaternary ammonium radical and the other a hydroxyl group.
  • these polymers contain, attached to carbon atoms of the linear polymeric chain a pluralityof extralinear units containing the group where Q represents a quaternary ammonium hywill bea polymer of the same structure except that the epoxy group in the side-chain has opened to. give. aside chain -in. which adjacent carbon atoms'bear a hydroxyl group and a quaternary ammonium group, respectively.
  • nitrogen-containing polymers have molecular weights above about 500, and the more useful ones range in molecular weights from about 1000 to about 10,000. Most of these polymers are soluble in either water or in dilute acid, e. g., 1-10%.aqueous acetic acid, and these soluble polymers are particularly useful and therefore preferred.
  • the polymers containing quaternary ammonium hydroxide groups are in general strongly basic. However, in cases where the vinylidene portion of the polymer contains hydrolyzable ester groups, for example, with products derived from allyl glycidyl ether/vinyl acetate copolymers, aqueous solution of the quaternary ammonium bases may be neutral or nearly so, presumably because of partial hydrolysis of the acetate groups by the strong base.
  • the polymeric quaternary ammonium hydroxides are preferably stored in aqueous or acid solutions, since the isloated free bases are sometimes unstable. Even the polymeric quaternary ammonium salts are preferably stored in solution, from which they can readily be isolated if desired.
  • the polymeric products of this invention are quite versatile and find uses in such various applications as antistatic coatings, emulsifying agents for wax, oil or insecticide dispersions, surface-modifiers for glass or silica, and, generally, as ingredients of film-forming coating and impregnating compositions. These products are widely useful as surface-active agents.
  • the acid-insoluble products which can be handled in organic solvent solutions, are useful as aciddyeable ingredients of fiber-forming polymeric compositions.
  • a polymeric quaternary ammonium compound v containing between 05% and. 5% nitrogen, by weight, said compoundibeing obtainedlby reacting acopolymer of allyl glycidyliethenv and -vinyl;. a.cetate, said. copolymen having; a molecular weight or 1,000 to 10,000 and containirig:0.6%
  • a.v tertiary monoaminev having: a basicitya equivalent to anionization constant.- of at least 1x10- 'anda-compound from the-group consistingiofrwateri and acids,- each in an amount oflat. least..0.25' equivalent per. oxirane-oxygen atom.
  • Process otpreparinga polymericquaternary ammoniumcompound which comprises reacting aecopolymen oiattinylidene: monomer free from epoxy groups and..an.ethy1enicallyunsaturated epoxy-group .containing..monomer, saidcopolymer.having.- a.molecular. weight of. 1.000rt0 (10,000 and containing 0.&%.to 7%.,rbyiweight of .oxirane oxygen. with-a tertiam .monoaminehavinga basicity. equivalent; to. an ionization constantrof atleast 1 10.”' in an amountibetweenmifizandj Bquivalents rpernoxirane oxygen. atom, andiascompoundiromrtheugroup consisting .of water. and acids; ineaneamount betweeninlifirand 5 equivalents per ox-irane oxxgenatom.
  • copolymer is acopolymer allyl .giycidyl. ether and vinyl acetate.-

Description

Patented Apr. 20, 1954 POLYMERIC QUATERNARY AMJWONIUM COMPOUNDS Vincent Joseph. Webers, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a. corporation of Delaware No Drawing. Application April 1, 1952, Serial No. 279,937
This invention relates to polymeric quaternary ammonium compounds and to a process of preparing same and, more particularly, to new poly meric quaternary ammonium compounds. Polymeric compounds containing quaternary ammonium hydroxide or salt groups are b'ecom-" ing of increasing technical interest in various applications such as, for example,acid -dyeable adjuvants to fiber-forming polymeric materials.
The study of quaternary ammonium polymers has, however, been greatly retarded by the few polymers of this type that are available and by the lack of satisfactory methods forpreparing them.
' An object of the present invention is to pro vide an economic processoi preparing polymeric quaternary ammonium 'comp'ounds'from readily available polymers in one operation. A further object is to provide new polymeric quaternary ammonium compounds. Other objects will be apparent from the description of theinvention' given hereinafter. v
The above objects are accomplished according to the present invention by reacting a copolymer of a vinylidene monomer free from epoxy groups and an ethylenically unsaturated epoxy -gro'up containing monomer, with a tertiary monoamine and either water or an acid or a combination of both. The resulting product is a copolymer con.- taining polymerized units of a vinylidene monomer free of epoxy groups and polymerized units of an ethylenically unsaturated epoxy monomer in which latter units the oxirane ring has opened to alpha-hydroxy-beta-quatemary ammonium groups. The resulting compound can also contain unreacted epoxy groups. These polymeric quaternary ammonium compounds are characterized by having at least 0.3% nitrogen, by weight, and a molecular weight of at least 500. In carrying out the reaction of the present invention the copolymer should have .a molecular weight above about 500 and contain from about 0.3% to about 8%, by weight, of oxirane oxygen and it should be reacted with a tertiary amine and with a compound HX in which X is hydroxyl or an anion, the tertiary amine and HK compound each being used in amounts of at least 0.25 equivalent per oxirane oxygen atom in the epoxy-containing copolymer.
It will be understood that an epoxygroup, also called oxirane group, is the group 7 The oxygen atom which is part of the oxirane group is re to, Q iIane o yg n. 4
6 Claims. --(c1. 260-855) The reaction involved in carrying out the process of the present invention may be represented by the following equation:
represents the epoxy groups contained in the copolymer, RcN is a tertiary monoamine and ED! is a compound wherein X is hydroxyl or an anion, i. e., HX is water or an inorganic or organic acid.
The polymeric compounds of this invention are quaternary ammonium hydroxides or salts, depending on whether the reactant I-lX is water or an'facid. They are resinous materials of viscous to semi-solid consistency and of indefinite melting point. Most of these compounds are soluble in dilute aqueous acids, e. g., aqueous acetic acid, and many of them are soluble in'water; In some instances, however, particularly when the starting copolymer has a low oxirane oxygen content, i. e., a low proportion of polymerized epoxy monomer, and/or when the degree'of substitution by the tertiary amine is low, the polymer is insoluble or only slightly soluble in dilute acids. In all cases, nevertheless, the polymers contain at least 0.3%, by weight, of nitrogen and this minimum proportion is necessary for significant modification of the starting copolymer. Preferably, the polymers contain between 0.5% and 5% of nitrogen.
The polymeric quaternary ammonium compounds of this invention have a. plurality of pairs of adjacent extralinear carbon atoms, one carbon atom of a pair carrying a quaternary ammonium radical and the other a hydroxyl group. Otherwise expressed, these compounds have a plurality of extralinear units containing the wherein Q is a quaternary ammonium radical. As previously stated, these compounds are further characterized by containing at least 0.3% nitrogen, by weight, and having a molecular weight of at least 500.
Preparation of these polymeric quaternary ammonium compounds can be conveniently carried out as follows: A solution, preferably at 25-75% m m tlQP: 9: 2 p q P9 Y in an organic solvent which is substantialy inert to the reactants used under the operating conditions, is treated with the tertiary amine, the amount of the latter being at least 0.25 equivalent, and preferably between 0.5 and 5 equivalents, per epoxy group. If desired, the amine is dissolved, preferably at -50% concentration, in an inert organic. solvent. This is particularly desirable when a volatile amine such as trimethylamine is used There is added to the reaction mixture water or an organic or inorganic acid in; amounts of at least 0.25 equivalent, and preferably between 0.25 and 5 equivalents, per epoxy group. If--desired, both water and an acid can be used simultaneously. The reaction mixture is usually, but. not necessarily, diluted to about solids by addition of an inert organic solvent, preferably one that is partly or completely miscible with water, such as methyl ethyl ketone or dioxane. The re- 4 g. of methyl ethyl ketone was mixed with 2.36 g. of trimethylamine in 12.2 g. of isopropyl alcohol (equivalent ratio of trimethylamine to oxirane 20:1) and with 0.72 g. of. water (equivalent ratio of water to oxirane 2.111).: The nnixture was diluted with 62 g. of dioxane and allowed to re- "act 10 days at room temperature. The reaction accordance withlthe'method just described, these examples are described in condensed form .for the sakeotbteyity. The following abbreviations are gused:
' AGE/VAc=allyl glycldyl ether/vinyl acetate action mixture is thenheld .at a suitable tem- 2o reaction product in dilute aqueous acid, e. g., 10%
' acetic acid, or in water, since the startingpolymers are insoluble in either medium. If the reaction product is insoluble in either dilute acid or water, asis sometimes the case when the start-'- ing material has a low content of epoxide groups,
the reaction product can .be. tested qualitatively orlquantitatively for the presence. of nitrogen. For. useful modification, the, reaction product shouldcontainatleast 0.3% nitrogen. l
Thereaction product is convenientlyisolated by either of two general procedures: (a) All solvents and volatile amine are removed by vacu-. umdistillation at low or. moderate temperature, eg.,v C. When the residuebecomes quite. viscous, some water may be added to thin it. out. and the distillation is .continueduntilthe residue reaches or' approaches the theoretical dry weight. The polymeric quaternary ammonium .baseor salt. is preferably stored as a 20-40% solution in water or diluteacetic ,acid, or as an organic solvent solution. (b) The reactionmixture is poured in':.' to a poor solventfor the quaternary ammonium" polymer, such as. ether, and theprecipitated nitrogen-containing polymer is stirred with ad ditional ether. The process may be repeated by redissolving the polymer inan appropriate sol vent andreprecipitating it with ether. The so].-
copolymer AGE/ S=a1lyl glycidyl ether/styrene copolymer eq.=equivalent I eq. ratio=equivalent ratio of tertiary amine or HX compound to oxirane oxygen present inthe opolyme M. w.=mo.lecular..we je t .Emempleifl I AGEW c; (M. ;W-.- 7000, 4.42%; AGE, 052%" oxirane oxygen) 9:61 g:"('0.'00373 oxirane--eq;)
5.4 g. dioxanQ-rriixd-with-OAQ- 'g-.- trimethylamine (eq. ratio 22:1) in- 2.5 --g,isopropyl alcohol and 0.15 g. water (eq. rati -2.2110,. YAdded24 ease,-
tone and reacted 2 days, room temperature. The product dissolved in. waterand precipitated pnaddition of sodium hydroxide. 'It slowly redis solved in dilute; acetic acid.
.Ex mele. III
AGiEI-VAc (M. w. 1000, 11.7% AGE, 1.64%
ox'irane oxygen-l, 12126 g. (0.0123 oxirane eq-.-) in Meg. methyl ethyl ketone, mixed with 1.47 g.
trimethylamine (eq. ratio 2:1), 03--g.='water- (eq. ratio 2.84:1) and 1.8 g. acetic acid (-eq'. ratio 254371). -Added31g.-di0xane and reacted 16 hours, room temperature. Product was-water- Example IV he's/vac. (M. w. about 200. 30.0% AGE.
-- 4.28%oxirane oxygen), 200g. (0.537oxi-rane-eq.)
a solution in a convenient solvent, particularly water if possible.
The following examples wherein all proportions are by weight unless otherwise stated, illustrate the preparation of specific polymeric quaternary ammonium compounds in accordance with .the present invention. The oxirane equivalen given in the examples can be defined as the decimal fraction of one equivalent (atom)' of oxirane oxygen present in-the weight of copolymer employed. It is given by the formula:
Weight of copolymer X oxirane oxygen per cent Example I I The starting material was an allyl glycidyl ether/vinyl acetate copolymer 'havinga mo'lecurlar weight of 3500 and containing 9.3%- ofpoly ind-9 g. methyl ethyl hetone, m-ixed with 35.4 ,g. trimethylamine (eq.;ratio 1.111) in 180 g. isopropylacloholand 32.2.;g.;-acetic acid (eq. ratio 1.11). .Reacted. A days, room temperature. Theproduct. -was: wateresoluble and neutral.
' Y Erazziple if AGE/VAC (M. W. 3360, 17.5% AGE, 2.45%.
oxirane oxygen) 192g. v(0.206 .oxirane eq.) in 108 g. dioxane, mixed with 8.74 'g. trimethylamine merized allyl glycidyl ether (118% oxyj gen). A solution of 24.1 g; of this copolymer (corresponding to-0.02 oxirane equivalent) in 15.9 -"l6 (eq. ratio 05:1) in 452g. isopropyl alcoholand 8.9 g. acetic acid (eq. ratio 0.521). Reacted 1 hou1:,'-100"- CZ, then 16 hours, room temperature. Reaction .product was water-soluble.
Example =VI AGE Wm (M'; w: about 1000, 913% AGE, 1.3% Y oxirane ox eer-gmr-wg.---(*0.'0111 oxirane eq.)
oxygen), 34.9 g. (0.0865 oxirane eq.) in 15.1 g.. xylene, mixed with 10.62 g. trimethylamine (eq.
Ezcample XXV i-vinylcyclohexene monoepoxide/vinyl acetate copolymer (M. W. 2200, 9.3% d-vinylcyclohexene monoepoxide, 1.2% oxirane oxygen), 10.0 g. (0.0075 oxirane eq.) in 10.0 g. methyl ethyl ketone, mixed with 0.89 g. trimethylamine (eq. ratio 2:1) in 4.6 g. isopropyl alcohol and 1.2 g. acetic acid (eq. ratio 2.66:1). Added 20.7 g. dioxane and reacted 4 hours at 80-85 C. The product was almost completely soluble in water and dilute acetic acid.
Example XXVI Glycidyl methacrylate/butyl methacrylate copolymer (M. W. 3500, 30% glycidyl methacrylate, 3.38% oxirane oxygen), 10.0 g. (0.0211 oxirane eq.) in 10.0 g. methyl isobutyl ketone, mixed with 2.95 g. trimethylamine (eq. ratio 2.13:1) in 15.25 g. isopropyl alcohol and 0.65 g. water (eq. ratio 1.7:1). Reacted 2 hours, room temperature. Product was water-soluble.
The foregoing examples are merely illustrative and the present invention broadly comprises reacting a copolymer of a vinylidene monomer free from epoxy groups and an ethylenically unsaturated epoxy-group containing monomer, with a tertiary monoamine and water or an acid, to form a polymeric quaternary ammonium compound containing at least 0.3% nitrogen and having a molecular weight of at least 500.
As starting material in the preparation of the polymeric quaternary ammonium compounds of this invention, there can be used any copolymer of a polymerizable, ethylenically unsaturated compound containing epoxy groups with a polymerizable' ethylenically unsaturated compound free from epoxy groups and in which copolymer the oxirane oxygen content is within the range of from about 0.3% to about 8%. Such copolymers offer a number of important technical advantages in the preparation of polymeric quaternary ammonium compounds. In the first place, it is pos-- sible with their use to obtain polymeric quaternary ammonium compounds of high molecular weight and, moreover, the molecular Weight is controllable to a large extent since the starting copolymers are made by free radical-initiated addition polymerization according to methods well understood in the art. In the second place,
polymers of the type defined above can be obtained which combine high molecular weight with high oxirane oxygen content, a combination which is not possible when using epoxy polymers such as, for example, those prepared by condensing dihydric phenols and epichlorohydrin in alkaline solution. In the third place, the starting copolymers are in general easy to prepare by wellknown methods and, in many cases, they ofi'er substantial economic advantages since the bulk of the weight can be derived from a cheap, readily available vinylidene monomer.
As already stated, the epoxy copolymer should contain at least about 0.3% of oxirane oxygen since, if the oxirane oxygen content is appreciably below that value, there will not be enough epoxy groups present to react effectively with the tertiary amine. On the other hand, if the polymerizable epoxy compound is present in the polymerization mixture in proportions such that the resulting copolymer has appreciably more than 8% of oxirane oxygen, then the polymerization becomes diflicult to carry out and control as, in.
many cases, unsaturated epoxy monomers do not polymerize well. Furthermore, the above-mentioned economic advantages are substantially lessened. Preferably, the starting copolymer contains between 0.6% and 7% of oxirane oxygen. copolymers within the desired range of oxirane.
oxygen content are generally obtained when the weight ratio of polymerized epoxy compound to polymerized oxirane-free unsaturate is within the range of 3:97 to 60:40.
The molecular weight of the copolymer is de sirably above 500 in order that the final products have the desired polymeric properties. As a consequence, the molecular weight of the final products will be at least 500. Preferably, the molecular weight of the copolymer is in the range of from about 1000 to about 10,000. The preferred copolymers have at least two epoxy groups per molecule.
The epoxide copolymers are prepared by free radical-initiated polymerization according to known methods and with known free radicalproducing initiators. to avoid conditions which would tend to open or otherwise destroy the epoxy groups, such as the presence of strong acids. In order to produce copolymers of the desired composition, the monomers are in general used in relative amounts within the range of 5 to 75 parts of oxirane-con taining unsaturate for to 25 parts of oxiranefree unsaturate.
Two or more comonomers of each type can be used provided the above ratios are observed.
In addition to the epoxide copolymers shown in I methacrylate, acrylamide, methacrylamide, acryl-.
onitrile, methacrylonitrile, styrene, 1,3-butadiene,
isoprene, 2-chloro-1,3-butadiene, vinyl chloride,
vinyl fluoride, isopropenyl acetate, vinylidene chloride, methyl vinyl ether, acrolein, methyl vinyl ketone, and the like. Preferably, these copolymers are made from monomers having only one ethylenic, carbon to carbon double bond, to
minimize the danger of cross-linking to insoluble" materials. These copolymers should obviously be prepared from monomers free from groups containing active hydrogen capable of reacting with an epoxide group.
The preferred starting materials, because they give the most generally useful polymeric quaternary ammonium compounds, are the copolymers of allyl glycidyl ether with polymerizable vinylidene compounds, i. e., compounds having a terminal methylene group attached through a double bond-to the adjacent carbon atom. These preferred materials include the copolymers of allyl glycidyl ether with the vinyl halides, e. g.,
vinyl chloride, vinyl fluoride; the vinyl esters of monocarboxylic acids, e. g., vinyl acetate, vinyl 1 methacrylamide; the monounsaturated hydro- I carbons having a terminal ethylenic double bond,
It is, of course, important 9 e. g.', isobu-tylene, styrene; and the like. Particularly preferred are the copolymers of vinyl ace- 4 tate and allyl glycidyl ether, especially those containing between 3% and 50% by weight of polymerized allyl glycidyl ether.
Any tertiary monoamine may be used to prepare the polymeric quaternary ammonium compounds, although it is preferred to use an amine of relatively low molecular weight, e. g., one containing a total of between 3 and 24 carbon atoms. The preferred amines are those in which the radicals attached to the amino nitrogen each contain from 1 to 6 carbon atoms, inclusive. Still more preferred are the ethylenically saturated amines containing only carbon and hydrogen in addition to the amino nitrogen. Suitable amines in addition to those shown in the examples, include tri-n-propylamine, tri-n-octylamine, N,N-
dimethylstearylamine, triallylamine; N,N-di-, methyloleylamine, N,N-dimethylcyclohexylamine,'
N.N-dimethylbenzylamine, 2-ethylpyridine', N ,N- dimethylnaphthylamine, and the like. The tertiary amine should preferably have a 'basicity equivalent to an ionization constant of at least 1 10. With weak bases in particular, it is advantageous to use an acid rather than water as the third reactant, in order to increase the reaction rate and bring the reaction time down to a convenient value, and to avoid degradation of the polymer which might be caused by prolonged heating.
For good results, the amine should be used in amount of at least 0.25 equivalent per oxirane oxygen atom in the epoxide-containing copolymer. Preferably, it is used in amounts between 0.5 and 5.0 equivalents per epoxy group. More can be used, if desired, but this is uneconomical and unnecessary.
The third reactant is water or an acid, leading to a polymeric quaternary ammonium hydroxide or salt. Any inorganic or organic acid can be used, including for example, hydrochloric, phosphoric, sulfuric, acetic, propionic, benzoic, and lactic acids. It is advantageous to use a cheap and common acid. Preferably, the acid is a monobasic acid having a dissociation constant of at least 1X10- An amine carbonate can sometimes be used advantageously. Water and an acid can be used simultaneously. The water and/or the acid should be used in amounts of at least 0.25 equivalent per epoxy group, and preferably between 0.5 and 3 equivalents. It is usually desirable to use the acid in amounts between 0.5 and 1.5 equivalents per equivalent of amine, since a large excess of acid relative to the amine might cause excessive opening of the epoxy groups in the polymer. Water can be used in large excess relative to the amine, although there is usually no advantage in doing so.
If the third reactant, i. e., water or acid, is omitted, either no reaction takes place during a reasonable period, or a reaction of an obscure nature takes place, leading to insoluble and infusible materials.
The process is carried out conveniently by bringing the three reactants in contact and allowing the reaction to proceed, preferably at a temperature in the range of 0 C. to 150 C., and still more preferably in the range of 15 C. to 100 C. The reaction time depends on the temperature to a considerable extent. As already noted, the reaction rate when weakly basic amines are used is accelerated by using an acid as the third reactant; rather than water. In most cases the progress of the reaction can be droxide or salt group. 'To illustrate, when the starting material is a copolymer containing as 10 followed by testing the solubility of the product in dilute acid or water. In other cases the product, after removal of the unchanged amine, can be tested qualitatively or quantitatively for the presence of nitrogen. For appreciable modification, the final product should contain at least 0.3% of nitrogen.
The products of this invention are polymers having a plurality of pairs of adjacent extralinear carbon atoms, one carbon atom of a pair carrying quaternary ammonium radical and the other a hydroxyl group. In other words, these polymers contain, attached to carbon atoms of the linear polymeric chain a pluralityof extralinear units containing the group where Q represents a quaternary ammonium hywill bea polymer of the same structure except that the epoxy group in the side-chain has opened to. give. aside chain -in. which adjacent carbon atoms'bear a hydroxyl group and a quaternary ammonium group, respectively.
These nitrogen-containing polymers have molecular weights above about 500, and the more useful ones range in molecular weights from about 1000 to about 10,000. Most of these polymers are soluble in either water or in dilute acid, e. g., 1-10%.aqueous acetic acid, and these soluble polymers are particularly useful and therefore preferred.
The polymers containing quaternary ammonium hydroxide groups are in general strongly basic. However, in cases where the vinylidene portion of the polymer contains hydrolyzable ester groups, for example, with products derived from allyl glycidyl ether/vinyl acetate copolymers, aqueous solution of the quaternary ammonium bases may be neutral or nearly so, presumably because of partial hydrolysis of the acetate groups by the strong base. The polymeric quaternary ammonium hydroxides are preferably stored in aqueous or acid solutions, since the isloated free bases are sometimes unstable. Even the polymeric quaternary ammonium salts are preferably stored in solution, from which they can readily be isolated if desired.
The polymeric products of this invention are quite versatile and find uses in such various applications as antistatic coatings, emulsifying agents for wax, oil or insecticide dispersions, surface-modifiers for glass or silica, and, generally, as ingredients of film-forming coating and impregnating compositions. These products are widely useful as surface-active agents. The acid-insoluble products which can be handled in organic solvent solutions, are useful as aciddyeable ingredients of fiber-forming polymeric compositions.
As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited l1 to;the.sp ecific embodimentsthereof except-aside finedinrthe apperidedclaims. V
The invention claimed'eis:
l. A polymeric quaternary ammonium compound v containing between 05% and. 5% nitrogen, by weight, said compoundibeing obtainedlby reacting acopolymer of allyl glycidyliethenv and -vinyl;. a.cetate, said. copolymen having; a molecular weight or 1,000 to 10,000 and=containirig:0.6%
to 7 by weighthvofl oxiranemxt'gen,v with a.
tertiary monoamine having .a basicity, equivalent to .an ionization constant of. atleast 1 '10* --in an amount between 0:5 :and 5. equivalents per oxirane oxygen-atomand :acompound from the group consisting -of twaterand; acids, in :an amount polymer is reacted with a: tentiary-monoamine=" containing three;'hydrocarbonrradicals ofijlzto: 6 carbon'atoms. inclusive, attachedrto-vthe-amino nitrogen.
3. A polymeric quaternary ammonium compound as set forth in claim 1, wherein said copolymer is reacted with a tertiary monoamine from the group consisting of 'trimethylamin'e and triethylamine.
4. Processof. preparing; a ,polymericquaternary ammonium :compoundwhich comprises: reacting" .ahcopolymer of. avinylidene monomer free from epoxy groups and. :amethylenically: unsaturated --en0xy-groupcontaining-monomers. said ;-copoly menhavingia molecular-weight ofat-least-fiflfland containing. 0.3%v to; 8.%,,by weight. of .oxirane ox-ygen,.--with a.v tertiary monoaminev having: a basicitya equivalent to anionization constant.- of at least 1x10- 'anda-compound from the-group consistingiofrwateri and acids,- each in an amount oflat. least..0.25' equivalent per. oxirane-oxygen atom.
5. Process otpreparinga polymericquaternary ammoniumcompound. which comprises reacting aecopolymen oiattinylidene: monomer free from epoxy groups and..an.ethy1enicallyunsaturated epoxy-group .containing..monomer,, saidcopolymer.having.- a.molecular. weight of. 1.000rt0 (10,000 and containing 0.&%.to 7%.,rbyiweight of .oxirane oxygen. with-a tertiam .monoaminehavinga basicity. equivalent; to. an ionization constantrof atleast 1 10."' in an amountibetweenmifizandj Bquivalents rpernoxirane oxygen. atom, andiascompoundiromrtheugroup consisting .of water. and acids; ineaneamount betweeninlifirand 5 equivalents per ox-irane oxxgenatom.
.6.' .Process as seti forthin claimjmhereinsaid copolymer is acopolymer allyl .giycidyl. ether and vinyl acetate.-
"References Cited in the; file of this patent UN ITEDF STATES RA'JZIENTS Number Name- Date i ;2;1!73;069.' Ulrich eta! 'Sept.:1Z 1939 I 2,556,075 Erickson June;-5;'-1951 $2562.89? Eilingboe' Aug-,:7;1951 ::2,581,392: :De'Groote: Jan-.8; 1952

Claims (1)

1. A POLYMERIC QUATERNARY AMMONIUM COMPOUND CONTAINING BETWEEN 0.5% AND 5% NITROGEN, BY WEIGHT, SAID COMPOUND BEING OBTAINED BY REACTING A COPOLYMER OF ALLYL GLYCIDYL ETHER AND VINYL ACETATE, SAID COPOLYMER HAVING A MOLECULAR WEIGHT OF 1,000 TO 10,000 AND CONTAINING 0.6% TO 7%, BY WEIGHT, OF OXIRANE OXYGEN, WITH A TERTIARY MONOAMINE HAVING A BASICITY EQUIVALENT TO AN IONIZATION CONSTANT OF AT LEAST 1X10-9 IN AN AMOUNT BETWEEN 0.5 TO 5 EQUIVALENTS PER OXIRANE OXYGEN ATOM, AND A COMPOUND FROM THE GROUP CONSISTING OF WATER AND ACIDS, IN AN AMOUNT BETWEEN 0.25 TO 5 EQUIVALENTS PER OXIRANE OXYGEN ATOM.
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US2884057A (en) * 1954-02-25 1959-04-28 American Cyanamid Co Paper of improved dry strength and method of making same
US2949445A (en) * 1958-05-06 1960-08-16 Du Pont Methyl methacrylate polymers containing amino residues
US2949383A (en) * 1958-05-06 1960-08-16 Du Pont Process of coating with methyl methacrylate composition therefore and article produced thereby
US2998415A (en) * 1955-12-15 1961-08-29 Universal Oil Prod Co Preparation of resinous materials from unsaturated ethers and heterocyclic compounds
US3000690A (en) * 1956-02-06 1961-09-19 Rohm & Haas New polymers of unsaturated glycidyl ethers and methods for producing them
US3028362A (en) * 1958-02-12 1962-04-03 Albert Ag Chem Werke Copolymerization of acrolein with an epoxy compound in the presence of a thioamide caalyst, and product obtained thereby
US3177171A (en) * 1959-10-08 1965-04-06 Gen Tire & Rubber Co Process for reacting ammonia or a primary amine with an acrolein polymer and resulting product
US3278474A (en) * 1962-06-20 1966-10-11 Shell Oil Co Copolymers of unsaturated aldehydes and quaternary ammonium compounds, derivatives thereof, preparation and use
US3321649A (en) * 1964-12-28 1967-05-23 Shell Oil Co Separation of suspended solids by cationic polymeric flocculants
US3323946A (en) * 1965-02-24 1967-06-06 Continental Can Co Method of preparing a coating composition
US3347832A (en) * 1964-10-29 1967-10-17 Shell Oil Co Cationic hydroxy-containing terpolymers, preparation and use
US3428617A (en) * 1964-10-19 1969-02-18 Shell Oil Co Cationic hydroxy-containing polymers,preparation and use
US3467624A (en) * 1963-06-03 1969-09-16 Bridgestone Tire Co Ltd Epoxide polymers and process for preparing same
US3468816A (en) * 1964-07-24 1969-09-23 Nalco Chemical Co Method of purifying an impure quaternary ammonium salt by addition of an epoxide
US3541059A (en) * 1967-04-19 1970-11-17 Calgon C0Rp Novel reaction products of glycidyl esters and alkali metal sulfite or bisulfite,and polymers thereof
US3684784A (en) * 1969-10-15 1972-08-15 Rhone Poulenc Sa Quaternary nitrogen-containing random copolymers
JPS4869896A (en) * 1971-12-20 1973-09-21
US3839252A (en) * 1968-10-31 1974-10-01 Ppg Industries Inc Quaternary ammonium epoxy resin dispersion with boric acid for cationic electro-deposition
US3936405A (en) * 1972-08-16 1976-02-03 Ppg Industries, Inc. Novel pigment grinding vehicles
US3937679A (en) * 1968-10-31 1976-02-10 Ppg Industries, Inc. Electrodepositable compositions
USB455686I5 (en) * 1972-08-03 1976-03-02
US3959106A (en) * 1974-03-27 1976-05-25 Ppg Industries, Inc. Method of electrodepositing quaternary sulfonium group-containing resins
US3962165A (en) * 1971-06-29 1976-06-08 Ppg Industries, Inc. Quaternary ammonium salt-containing resin compositions
US3975346A (en) * 1968-10-31 1976-08-17 Ppg Industries, Inc. Boron-containing, quaternary ammonium salt-containing resin compositions
US4009133A (en) * 1975-08-01 1977-02-22 Ppg Industries, Inc. Electrodepositable epoxy resins having quaternary groups carrying blocked NCO, and aqueous dispersions
US4038232A (en) * 1972-12-19 1977-07-26 Ppg Industries, Inc. Electrodepositable compositions containing sulfonium resins and capped polyisocyanates
US4040924A (en) * 1975-08-01 1977-08-09 Ppg Industries, Inc. Aqueous cationic electrodeposition of epoxy resins having quaternary groups carrying blocked NCO
US4076676A (en) * 1975-02-04 1978-02-28 E. I. Du Pont De Nemours And Company Aqueous coating composition from aminoplast and reaction product of tertiary amine and polymer containing terminal epoxy groups
US4076675A (en) * 1975-02-04 1978-02-28 E. I. Du Pont De Nemours And Company Aqueous coating composition from aminoplast and reaction product of tertiary amine and polymer containing randomly distributed epoxy groups
US4081341A (en) * 1976-11-24 1978-03-28 Ppg Industries, Inc. Use of polymeric quaternary ammonium hydroxides in electrodeposition
US4101486A (en) * 1975-03-26 1978-07-18 Ppg Industries, Inc. Cationic electrodepositable compositions
US4102863A (en) * 1976-11-24 1978-07-25 Ppg Industries, Inc. Cationic electrodeposition using aqueous dispersions of quaternary ammonium carbonate-containing polymers
US4110287A (en) * 1975-03-21 1978-08-29 Ppg Industries, Inc. Cataphoretic N-heterocyclic-containing resins for electrodeposition
FR2416927A1 (en) * 1978-02-13 1979-09-07 Du Pont Thermosetting aq. coating compsn. - comprises epoxy! resin and alkylated amine aldehyde resin, partic. for coating food cans
US4170579A (en) * 1976-11-24 1979-10-09 Ppg Industries, Inc. Coating compositions comprising aqueous dispersions of quaternary ammonium base group-containing polymers and a curing agent
WO1980001071A1 (en) * 1978-11-22 1980-05-29 Grow Group Inc Cationic coating compositions
US4247439A (en) * 1973-11-06 1981-01-27 E. I. Du Pont De Nemours And Company Water-borne coating composition made from epoxy resin, polymeric acid and tertiary amine
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US4303488A (en) * 1973-11-06 1981-12-01 E. I. Du Pont De Nemours And Company Electrocoating with water-borne coating composition made from epoxy resin, polymeric acid and tertiary amine
US4339368A (en) * 1978-11-22 1982-07-13 Wyandotte Paint Products Company Cationic coating compositions containing nitrogen heterocyclic materials
US4383073A (en) * 1981-08-20 1983-05-10 The Dow Chemical Company Cationic resin curable with acid catalyzed cross-linkers
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US4689217A (en) * 1983-10-07 1987-08-25 Ici Americas Inc. Amine and ammonium nitrogen containing polyvinyl alcohol polymers having improved lipophilic properties for use in skin conditioning, cosmetic and pharmaceutical formulations
US4690817A (en) * 1983-10-07 1987-09-01 Ici Americas Inc. Quaternary nitrogen containing polyvinyl alcohol polymers for use in skin conditioning, cosmetic and pharmaceutical formulations
US4839203A (en) * 1985-04-03 1989-06-13 The Dow Chemical Company Semi-permeable membranes prepared via reaction of cationic groups with nucleophilic groups
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Cited By (57)

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US2884057A (en) * 1954-02-25 1959-04-28 American Cyanamid Co Paper of improved dry strength and method of making same
US2866779A (en) * 1954-07-23 1958-12-30 Phillips Petroleum Co Polymeric 2-hydroxyalkyl quaternary salts and process for their production
US2998415A (en) * 1955-12-15 1961-08-29 Universal Oil Prod Co Preparation of resinous materials from unsaturated ethers and heterocyclic compounds
US3000690A (en) * 1956-02-06 1961-09-19 Rohm & Haas New polymers of unsaturated glycidyl ethers and methods for producing them
US3028362A (en) * 1958-02-12 1962-04-03 Albert Ag Chem Werke Copolymerization of acrolein with an epoxy compound in the presence of a thioamide caalyst, and product obtained thereby
US2949445A (en) * 1958-05-06 1960-08-16 Du Pont Methyl methacrylate polymers containing amino residues
US2949383A (en) * 1958-05-06 1960-08-16 Du Pont Process of coating with methyl methacrylate composition therefore and article produced thereby
US3177171A (en) * 1959-10-08 1965-04-06 Gen Tire & Rubber Co Process for reacting ammonia or a primary amine with an acrolein polymer and resulting product
US3278474A (en) * 1962-06-20 1966-10-11 Shell Oil Co Copolymers of unsaturated aldehydes and quaternary ammonium compounds, derivatives thereof, preparation and use
US3467624A (en) * 1963-06-03 1969-09-16 Bridgestone Tire Co Ltd Epoxide polymers and process for preparing same
US3468816A (en) * 1964-07-24 1969-09-23 Nalco Chemical Co Method of purifying an impure quaternary ammonium salt by addition of an epoxide
US3428617A (en) * 1964-10-19 1969-02-18 Shell Oil Co Cationic hydroxy-containing polymers,preparation and use
US3347832A (en) * 1964-10-29 1967-10-17 Shell Oil Co Cationic hydroxy-containing terpolymers, preparation and use
US3321649A (en) * 1964-12-28 1967-05-23 Shell Oil Co Separation of suspended solids by cationic polymeric flocculants
US3323946A (en) * 1965-02-24 1967-06-06 Continental Can Co Method of preparing a coating composition
US3541059A (en) * 1967-04-19 1970-11-17 Calgon C0Rp Novel reaction products of glycidyl esters and alkali metal sulfite or bisulfite,and polymers thereof
US3839252A (en) * 1968-10-31 1974-10-01 Ppg Industries Inc Quaternary ammonium epoxy resin dispersion with boric acid for cationic electro-deposition
US3937679A (en) * 1968-10-31 1976-02-10 Ppg Industries, Inc. Electrodepositable compositions
US3975346A (en) * 1968-10-31 1976-08-17 Ppg Industries, Inc. Boron-containing, quaternary ammonium salt-containing resin compositions
US3684784A (en) * 1969-10-15 1972-08-15 Rhone Poulenc Sa Quaternary nitrogen-containing random copolymers
US3962165A (en) * 1971-06-29 1976-06-08 Ppg Industries, Inc. Quaternary ammonium salt-containing resin compositions
JPS4869896A (en) * 1971-12-20 1973-09-21
JPS523678B2 (en) * 1971-12-20 1977-01-29
USB455686I5 (en) * 1972-08-03 1976-03-02
US4001156A (en) * 1972-08-03 1977-01-04 Ppg Industries, Inc. Method of producing epoxy group-containing, quaternary ammonium salt-containing resins
US3936405A (en) * 1972-08-16 1976-02-03 Ppg Industries, Inc. Novel pigment grinding vehicles
US4038232A (en) * 1972-12-19 1977-07-26 Ppg Industries, Inc. Electrodepositable compositions containing sulfonium resins and capped polyisocyanates
US4303488A (en) * 1973-11-06 1981-12-01 E. I. Du Pont De Nemours And Company Electrocoating with water-borne coating composition made from epoxy resin, polymeric acid and tertiary amine
US4247439A (en) * 1973-11-06 1981-01-27 E. I. Du Pont De Nemours And Company Water-borne coating composition made from epoxy resin, polymeric acid and tertiary amine
US3959106A (en) * 1974-03-27 1976-05-25 Ppg Industries, Inc. Method of electrodepositing quaternary sulfonium group-containing resins
US4076676A (en) * 1975-02-04 1978-02-28 E. I. Du Pont De Nemours And Company Aqueous coating composition from aminoplast and reaction product of tertiary amine and polymer containing terminal epoxy groups
US4076675A (en) * 1975-02-04 1978-02-28 E. I. Du Pont De Nemours And Company Aqueous coating composition from aminoplast and reaction product of tertiary amine and polymer containing randomly distributed epoxy groups
US4110287A (en) * 1975-03-21 1978-08-29 Ppg Industries, Inc. Cataphoretic N-heterocyclic-containing resins for electrodeposition
US4101486A (en) * 1975-03-26 1978-07-18 Ppg Industries, Inc. Cationic electrodepositable compositions
US4040924A (en) * 1975-08-01 1977-08-09 Ppg Industries, Inc. Aqueous cationic electrodeposition of epoxy resins having quaternary groups carrying blocked NCO
US4009133A (en) * 1975-08-01 1977-02-22 Ppg Industries, Inc. Electrodepositable epoxy resins having quaternary groups carrying blocked NCO, and aqueous dispersions
US4141810A (en) * 1976-11-24 1979-02-27 Ppg Industries, Inc. Cationic electrodeposition using aqueous dispersions of quaternary ammonium carbonate-containing polymers
US4170579A (en) * 1976-11-24 1979-10-09 Ppg Industries, Inc. Coating compositions comprising aqueous dispersions of quaternary ammonium base group-containing polymers and a curing agent
US4102863A (en) * 1976-11-24 1978-07-25 Ppg Industries, Inc. Cationic electrodeposition using aqueous dispersions of quaternary ammonium carbonate-containing polymers
US4081341A (en) * 1976-11-24 1978-03-28 Ppg Industries, Inc. Use of polymeric quaternary ammonium hydroxides in electrodeposition
FR2416927A1 (en) * 1978-02-13 1979-09-07 Du Pont Thermosetting aq. coating compsn. - comprises epoxy! resin and alkylated amine aldehyde resin, partic. for coating food cans
WO1980001071A1 (en) * 1978-11-22 1980-05-29 Grow Group Inc Cationic coating compositions
US4246087A (en) * 1978-11-22 1981-01-20 Grow Group, Inc. Process for cationic electrodeposition
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